U.S. patent number 8,889,785 [Application Number 13/391,467] was granted by the patent office on 2014-11-18 for production method of thermoplastic resin composition, molded body, and light emission body.
This patent grant is currently assigned to Mitsubishi Rayon Co., Ltd.. The grantee listed for this patent is Hiroshi Niino, Mitsufumi Nodono. Invention is credited to Hiroshi Niino, Mitsufumi Nodono.
United States Patent |
8,889,785 |
Niino , et al. |
November 18, 2014 |
Production method of thermoplastic resin composition, molded body,
and light emission body
Abstract
Disclosed is a production method of a thermoplastic resin
composition which has a good light emission property of visible
light by ultraviolet irradiation, the production method comprising:
compounding 0.001 to 50 parts by mass of at least one of metal
compound (B) selected from a metal complex (B1) and a metal halide
(B2), and 0.001 to 30 parts by mass of a polyalkylene glycol
compound (C), with respect to 100 parts by mass of a thermoplastic
resin (A); and heating it at a temperature of 100 to 320.degree.
C.
Inventors: |
Niino; Hiroshi (Hiroshima,
JP), Nodono; Mitsufumi (Hiroshima, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Niino; Hiroshi
Nodono; Mitsufumi |
Hiroshima
Hiroshima |
N/A
N/A |
JP
JP |
|
|
Assignee: |
Mitsubishi Rayon Co., Ltd.
(Tokyo, JP)
|
Family
ID: |
43607108 |
Appl.
No.: |
13/391,467 |
Filed: |
August 19, 2010 |
PCT
Filed: |
August 19, 2010 |
PCT No.: |
PCT/JP2010/063974 |
371(c)(1),(2),(4) Date: |
May 04, 2012 |
PCT
Pub. No.: |
WO2011/021658 |
PCT
Pub. Date: |
February 24, 2011 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20120214922 A1 |
Aug 23, 2012 |
|
Foreign Application Priority Data
|
|
|
|
|
Aug 20, 2009 [JP] |
|
|
2009-190963 |
Jan 6, 2010 [JP] |
|
|
2010-001246 |
|
Current U.S.
Class: |
524/560; 524/366;
524/413 |
Current CPC
Class: |
C08L
71/02 (20130101); C09K 11/02 (20130101); C08J
3/203 (20130101); C09K 2211/14 (20130101) |
Current International
Class: |
C08K
5/06 (20060101); C08K 3/16 (20060101); C08L
33/12 (20060101); C08K 3/10 (20060101); C08L
33/10 (20060101); C08L 33/08 (20060101) |
Field of
Search: |
;524/366,378,413 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
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|
|
2233976 |
|
Mar 1999 |
|
CA |
|
1 883 124 |
|
Jan 2008 |
|
EP |
|
2 067 839 |
|
Jun 2009 |
|
EP |
|
10 072552 |
|
Mar 1998 |
|
JP |
|
2005 096421 |
|
Apr 2005 |
|
JP |
|
2007 185924 |
|
Jul 2007 |
|
JP |
|
2008 238408 |
|
Oct 2008 |
|
JP |
|
2007 138970 |
|
Dec 2007 |
|
WO |
|
Other References
Machine translation of JP 10-072552 A (Mar. 17, 1998). cited by
examiner .
International Search Report issued Sep. 28, 2010 in
PCT/JP2010/063974 filed Aug. 19, 2010. cited by applicant .
U.S. Appl. No. 13/504,492, filed Apr. 27, 2012, Niino. cited by
applicant .
Search Report in corresponding European application No.
10809999.5-1306, mailed on May 27, 2014. cited by applicant .
Database WPI, Thomson Scientific, London, GB; An 1992-154569,
XP-002724132 & JPH04-91136, Mar. 24, 1992. cited by
applicant.
|
Primary Examiner: Nguyen; Vu A
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier
& Neustadt, L.L.P.
Claims
What is claimed is:
1. A method of producing an acrylic resin (A) composition
comprising: compounding 0.001 to 50 parts by mass of metal compound
(B) comprising a metal halide (B2), and 0.001 to 30 parts by mass
of a polyalkylene glycol compound (C), with respect to 100 parts by
mass of the acrylic resin (A); and heating them at a temperature of
100 to 320.degree. C.
2. The method of claim 1, wherein the metal of the metal compound
(B) is zinc.
3. The method of claim 1, wherein the acrylic resin (A) is selected
from the group consisting of polymethyl methacrylates, acrylic
resins obtained by copolymerization of methyl methacrylate with one
or more additional monomers, polymers containing acrylates or
methacrylates as a main component, acrylic resins obtained by graft
copolymerization of a polymer containing a rubber, with at least
one additional monomer, and mixtures thereof.
4. The method of claim 1, wherein the acrylic resin (A) has a mass
average molecular weight of 1,000 to 1,000,000.
5. The method of claim 1, wherein the acrylic resin (A) has a mass
average molecular weight of 5,000 to 800,000.
6. The method of claim 1, wherein the acrylic resin (A) has a mass
average molecular weight of 10,000 to 500,000.
7. The method of claim 1, wherein the metal compound (B) comprises
the metal complex (B1).
8. The method of claim 1, wherein the polyalkylene glycol compound
(C) is selected from the group consisting of polyalkylene glycols,
polyalkylene glycol monoalkyl ethers, polyalkylene glycol dialkyl
ethers and mixtures thereof.
9. The method of claim 1, further comprising molding the acrylic
resin composition to obtain a molded body.
10. The method of claim 2, further comprising molding the acrylic
resin composition to obtain a molded body.
11. The method of claim 9, further comprising incorporating the
molded body into a light emission body.
Description
TECHNICAL FIELD
The present invention relates to a production method of a
thermoplastic resin composition, a molded body obtained by molding
a thermoplastic resin composition which is obtained by the
production method, and a light emission body using the molded
body.
BACKGROUND ART
It is known that some metal oxides and metal complexes emit a
visible light by receiving irradiation of an ultraviolet. Using
this property, the metal oxides and metal complexes are used for an
optical material such as a fluorescent body.
The light emission property of the metal oxide and metal complex is
thought to be due to the crystal condition and an electron donor
type defect in the surface (a hole of interstitial metal and
oxygen). It is known that metal oxides in high crystal condition
and metal oxides in the surface of which an electron donor type
defect is generated emit a visible light by receiving irradiation
of an ultraviolet. Also, it is known that metal complexes emit a
light when it returns to the ground state from the excited state in
which is excited by receiving irradiation of an ultraviolet.
A thermoplastic resin composition containing a metal oxide is
generally produced by kneading metal oxide fine particles and a
thermoplastic resin, and is strongly influenced by particle
diameter and aggregation state of the metal oxide fine particles.
If the particle diameter is large, light emission intensity is
reduced or light emission is not provided. If aggregation of fine
particles is progressed, light emission intensity is reduced or
light emission is not provided.
In order to solve the problem, Patent document 1 proposes a
production method of a thermoplastic resin composition in which a
thermoplastic resin and a metal complex is heated. The molded body
obtained by this method has ultraviolet absorptivity. This molded
body may emit a visible light by receiving irradiation of an
ultraviolet, but the emission intensity is not high.
PRIOR ART DOCUMENT
Patent Document
Patent document 1: JP 10-72552 A
SUMMARY OF THE INVENTION
Problem to be Solved by the Invention
An object of the present invention is to provide a production
method of a thermoplastic resin composition and a molded body
thereof, which have a good light emission property of visible light
by ultraviolet irradiation.
Means of Solving the Problem
The present invention is a production method of a thermoplastic
resin composition comprising: compounding 0.001 to 50 parts by mass
of at least one of metal compound (B) selected from a metal complex
(B1) and a metal halide (B2), and 0.001 to 30 parts by mass of a
polyalkylene glycol compound (C), with respect to 100 parts by mass
of a thermoplastic resin (A); and heating it at a temperature of
100 to 320.degree. C.
Also, the present invention is a molded body obtained by molding a
thermoplastic resin composition which is obtained by the production
method.
Further, the present invention is a light emission body using the
molded body.
Effect of the Invention
According to the present invention, provided is a molded body which
has a good light emission property of visible light by ultraviolet
irradiation. That is to say, provided is a molded body in which the
wavelength of light is made long by light irradiation and in which
the light emission intensity is high.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is light emission spectra of molded bodies at an excitation
wavelength of 365 nm.
MODE FOR CARRYING OUT THE INVENTION
As a thermoplastic resin (A) of the present invention, a well-known
thermoplastic resin can be used. Examples thereof include, for
example, acrylic resins, styrene resins, olefin resins,
polycarbonate resins, polyvinyl chloride resins, polyvinylidene
chloride resins, polyimide resins, polyester resins, polyacetal
resins, polyphenylene ether resins, polyethylene terephthalate
resins, polybutylene terephthalate resins, polyarylate resins,
polyphenylene sulfide resins, polyethersulfone resins,
polyetherimide resins, polyether ether ketone resins, polyether
ketone resins, and fluorine resins. This thermoplastic resin (A)
may be used alone, or in combination with two or more kinds.
Among these thermoplastic resins (A), acrylic resins, styrene
resins, olefin resins, polycarbonate resins, polyvinyl chloride
resins, and polyester resins are preferable because they are melted
in a temperature range of 100 to 320.degree. C. Acrylic resins,
styrene resins, olefin resins, and polycarbonate resins are more
preferable. Also, acrylic resins, styrene resins, polycarbonate
resins are furthermore preferable because they have a good
compatibility with a polyalkylene glycol compound (C). Acrylic
resins are particularly preferable because the molded body obtained
has a good light emission property.
Examples of the acrylic resin include, for example, polymethyl
methacrylates (PMMA); acrylic resins obtained by copolymerization
of methyl methacrylate with another monomer such as styrene,
.alpha.-methyl styrene, acrylonitrile, and various acrylates or
methacrylates; polymers containing various acrylates or
methacrylates as a main component; and acrylic resins obtained by
graft copolymerization of a polymer containing a rubber such as
acrylic rubbers, silicone rubbers, and butadiene rubbers, with
another monomer such as methyl methacrylate, and various acrylates
or methacrylate.
Examples of the styrene resin include, for example, polystyrenes
(PS), high impact polystyrenes (HIPS), methyl methacrylate-styrene
copolymers (MS), methyl methacrylate-butadiene-styrene copolymers
(MBS), styrene-maleic anhydride copolymers (SMA),
styrene-methacrylic acid copolymers (SMAA), styrene-.alpha.-methyl
styrene copolymers, styrene-maleimide copolymers,
acrylonitrile-styrene copolymers, .alpha.-methyl
styrene-acrylonitrile copolymers, and alloys of this styrene resin
with a polyphenylene ether resin.
Examples of the acrylonitrile-styrene copolymer include, for
example, acrylonitrile-styrene copolymers (SAN),
acrylonitrile-styrene-butadiene copolymers (ABS),
acrylonitrile-styrene-acrylic rubber copolymers (AAS),
acrylonitrile-styrene-chlorinated polyethylene copolymers (ACS),
acrylonitrile-styrene-ethylene-propylene rubber copolymers (AES),
and acrylonitrile-styrene-ethylene-vinyl acetate copolymers. Also,
acrylonitrile-.alpha.-methyl styrene copolymers in which a styrene
moiety is substituted with .alpha.-methyl styrene are included.
Examples of the olefin resin include, for example, polyethylene
resins such as ultralow density polyethylenes, low density
polyethylenes, linear low density polyethylenes, medium density
polyethylenes, and high density polyethylenes; ethylene-vinyl
acetate copolymers having a vinyl acetate unit content of 0.1 to
25% by mass; ethylene-acrylic acid copolymers having an acrylic
acid unit content of 0.1 to 25% by mass; polypropylenes;
ethylene-propylene block copolymers having an ethylene unit content
2 to 40% by mass; ethylene-propylene random copolymers having an
ethylene unit content 0.5 to 10% by mass; polybutenes;
ethylene-propylene rubbers; ethylene-propylene-diene rubbers; and
cycloolefin resins (COP). Among these olefin resins, cycloolefin
resins (COP), low density polyethylenes, high density
polyethylenes, and polypropylenes are preferable because the molded
body obtained has a good mechanical property.
Examples of polyvinyl chloride resin include, for example, vinyl
chloride homopolymers; copolymers obtained by copolymerization of
vinyl chloride with another monomer such as ethylene, propylene,
acrylonitrile, vinylidene chloride, and vinyl acetate; and modified
polyvinyl chloride resins in which MBS, ABS, a nitrile rubber, a
chlorinated polyethylene, an ethylene vinyl alcohol-vinyl chloride
graft copolymer, or various plasticizers is added to a polyvinyl
chloride.
The mass average molecular weight of a thermoplastic resin (A) is
preferably 1,000 to 1,000,000, more preferably 5,000 to 800,000,
and furthermore preferably 10,000 to 500,000. When the mass average
molecular weight of a thermoplastic resin (A) is 1,000 or more, the
molded body obtained comes to have a good mechanical property.
Also, when the mass average molecular weight of a thermoplastic
resin (A) is 1,000,000 or less, the thermoplastic resin composition
has a good moldability, whereby the metal oxide comes to be
dispersed well in the molded body and the molded body obtained
comes to have a high light emission intensity.
A metal compound (B) of the present invention is at least one
compound selected from a metal complex (B1) and a metal halide
(B2).
The kind of a metal of a metal compound (B) is any of elements
which belong to Group 1 except for hydrogen, Group 2, Group 3
containing lanthanoid and actinoid, Group 4, Group 5, Group 6,
Group 7, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13
except for boron, Group 14 except for carbon, Group 15 except for
nitrogen, phosphorus and arsenic, and Group 16 except for oxygen,
sulfur, selenium and tellurium, in the periodic table. Examples
thereof include, for example, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr,
Ba, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,
Lu, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co,
Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, TI, Si, Ge,
Sn, Pb, Sb, and Bi. This metal can appropriately be chosen in view
of the semiconductor property of the metal oxide and the light
emission property of the molded body obtained. Also, this metal may
be used alone, or in combination with two or more kinds.
Among these metals, Zn, Al, Be, Dy, Eu, Sr, In, Yb, Co, and Ga are
preferable because the molded body obtained has a good light
emission property. Zn is more preferable.
Examples of the kind of a ligand which is bonded to a metal of a
metal complex (B1) include, for example, carboxylic acids,
.beta.-diketones, keto esters, hydroxy carboxylic acids or the
salts thereof, various Schiff bases, keto alcohols, polyvalent
amines, alkanolamines, enol-type active hydrogen compounds,
dicarboxylic acids, glycols, and ferrocenes.
Examples of the compound as a ligand which is bonded to a metal of
a metal complex (B1) include, for example, formic acid, acetic
acid, propionic acid, acetylacetone, tetrafluoroacetylacetone,
ethylenediamine, triethylenediamine, ethylenetetramine,
bispiperidine, cyclohexanediamine, tetraazacyclotetradecane,
ethylenediamine tetraacetic acid, ethylenebis(guanide),
ethylenebis(salicylamine), tetraethylene glycol, diethanolamine,
triethanolamine, tartaric acid, glycine, triglycine, naphthyridine,
phenanthroline, pentanediamine, salicylaldehyde, catechol,
porphyrin, thiourea, 8-hydroxyquinoline, 8-hydroxychinaldine,
.beta.-aminoethyl mercaptan, bisacetylacetone ethylenediimine,
Eriochrome Black T, oxine, quinaldinic acid salicylaldoxime,
picolinic acid, dimethylglyoximato, dimethylglyoxime,
.alpha.-benzoin oxime,
N,N'-bis(1-methyl-3-oxobutylidene)ethylenediamine,
3-{(2-aminoethyl)amino}-1-propanol, 3-(aminoethylimino)-2-butane
oxime, alanine, N,N'-bis(2-aminobenzylidene)ethylenediamine,
.alpha.-Amino-.alpha.-methylmalonic acid,
2-{(3-aminopropyl)amino}ethanol, aspartic acid,
1-phenyl-1,3,5-hexanetrione,
5,5'-(1,2-ethanediyldinitro)bis(1-phenyl-1,3-hexanedione),
1,3-bis{bis[2-(1-ethylbenzimidazolyl)methyl]amino}-2-propanol,
1,2-bis(pyridine-.alpha.-aldimino)ethane,
1,3-bis{bis(2-pyridylethyl)aminomethyl}benzene,
1,3-bis{bis(2-pyridylethyl)aminomethyl}phenol,
2,6-bis{bis(2-pyridylmethyl)aminomethyl}-4-methylphenol,
2,2'-bipyridine, 2,2'-bipyrazine, hydrotris(1-pyrazolyl)borate ion,
3,4:9,10-dibenzo-1,5,8,12-tetraazacyclotetradecane-1,11-diene,
2,6-diacetylpyridine dioxime, dibenzyl sulfide,
N-{2-(diethylamino)ethyl}-3-amino-1-propanol,
o-phenylenebis(dimethylphosphine),
2-{2-(dimethylamino)ethylthio}ethanol,
4,4'-dimethyl-2,2'-bipyridine,
N,N'-dimethyl-1,2-cyclohexanediamine,
1,2-bis(dimethylphosphino)ethane, 1,3-bis(diacetyl
monoximeimino)propane, 3,3'-trimethylenedinitrobis(2-butane
oxime)-1,5-diamino-3-pentanol dipivaloylmethane,
1,2-bis(diphenylphosphino)ethane, diethyldithiocarbamic acid ion,
N,N'-bis{2-(N,N'-diethylaminoethyl)aminoethyl}oxamide,
7-hydroxy-4-methyl-5-azahept-4-en-2-one, 2-aminoethanol,
N,N'-ethylenebis(3-carboxysalicylideneamine),
1,3-bis(3-formyl-5-methylsalicylideneamino)propane,
3-glycylamino-1-propanol, glycylglycine,
N'-(2-hydroxyethyl)ethylenediamine triacetic acid,
hexafluoroacetylacetone, histidine,
5,26:13,18-diimino-7,11:20,24-dinitrodibenzo[c,n]-1,6,12,17-tetraazacyclo-
docosyne, 2,6-bis{N-(2-hydroxyphenyl]iminomethyl}-4-methylphenol,
5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-N,N''-diaceti-
c acid, 1,2-dimethylimidazole,
3,3'-ethylenebis(iminomethylidyne)-di-2,4-pentanedione,
N,N'-bis(5-amino-3-hydroxypentyl)malonamide, methionine,
2-hydroxy-6-methylpyridine, methyliminodiacetic acid,
1,1-dicyanoethylene-2,2-dithiol, 1,8-naphthyridine,
3-(2-hydroxyethylimino)-2-butanone oxime,
2,3,7,8,12,13,17,18-octaethylporphyrin,
2,3,7,8,12,13,17,18-octamethylporphyrin, oxalic acid, oxamide,
2-pyridylaldoxime, 3-{2-(2-pyridyl)ethylamino}-1-propanol,
3-(2-pyridylethylimino)-2-butanone oxime, 2-picolylamine,
3-(2-pyridylmethylimino)-2-butanone oxime, phosphorous acid
dihydrogen ion, 3-n-propylimino-2-butanone oxime, proline,
pyridine, N,N'-dipyridoxylideneethylenediamine,
N-pyridoxylideneglycine, pyridine-2-thiol,
1,5-bis(salicylideneamino)-3-pentanol, salicylaldehyde,
N-salicylidene methylamine, salicylic acid,
N-(salicylidene)-N'-(1-methyl-3-oxobutylidene)ethylenediamine,
salicylideneamine, N,N'-disalicylidene-2,2'-biphenylylenediamine,
N, N'-disalicylidene-2-methyl-2-(2-benzylthioethyl)ethylenediamine,
N,N'-disalicylidene-4-aza-1,7-heptanediamine,
N,N'-disalicylideneethylenediamine, N-salicylideneglycine,
salicylaldoxime, N,N'-disalicylidene-o-phenylenediamine,
N,N'-disalicylidenetrimethylenediamine,
3-salicylideneamino-1-propanol,
tetrabenzo[b,f,j,n]-1,5,9,13-tetraazacyclohexadecyne,
1,4,7-triazacyclononane,
5,14-dihydrodibenzo[b,i]-1,4,8,11-tetraazacyclotetradecine,
tris(2-benzimidazolylmethyl)amine,
6,7,8,9,16,17,18,19-octahydrodicyclohepta[b,j]-1,4,8,11-tetraazacyclotetr-
adecene, 4,6,6-trimethyl-3,7-diazanon-3-ene-1,9-diol,
tris(3,5-dimethyl-1-pyrazolylmethyl)amine, 2,2':6',2''-terpyridine,
5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane,
tetrahydrofuran, tris(2-pyridylmethyl)amine,
N,N,N',N'-tetramethylurea, N,N'-bis(3-aminopropyl)oxamide,
N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine,
allcis-5,10,15,20-tetrakis{2-(2,2'-dimethylpropionamide)phenyl}porphyrin,
5,10,15,20-tetraphenylporphyrin,
1,4,7-tris(2-pyridylmethyl)-1,4,7-triazacyclononane,
hydrotris(1-pyrazolyl)borate, 3,3',4-trimethyldipyrromethene,
trimethylenediamine tetraacetic acid, 3,3',5,5'-tetramethyl
dipyrromethene, and 5,10,15,20-tetrakis(p-triporphyrin). This
compound as a ligand may be used alone, or in combination with two
or more kinds.
Among these compounds as a ligand, acetic acid, acetylacetone,
hexafluoroacetylacetone, ethylenediamine, bispiperidine,
bipyrazine, cyclohexanediamine, tetraazacyclotetradecane,
ethylenediamine tetraacetic acid, ethylenebis(guanide),
ethylenebis(salicylamine), tetraethylene glycol, aminoethanol,
glycine, triglycine, pentanediamine, pyridine, and thiourea are
preferable because the molded body obtained has a good light
emission property. Also, acetylacetone and acetic acid are more
preferable because they have a sublimation property and accelerate
the decomposition of a metal complex (B1) to a metal oxide.
Acetylacetone is furthermore preferable.
Examples of the halogen element which is bonded to a metal of a
metal halide (B2) include, for example, fluorine, chlorine,
bromine, and iodine. This halogen element may be used alone, or in
combination with two or more kinds. Among these halogen elements,
chlorine and bromine are preferable because the molded body
obtained has a good light emission property. Chlorine is more
preferable.
This metal compound (B) may be used alone, or in combination with
two or more kinds.
Among these metal compounds (B), they preferably have a high
solubility to a thermoplastic resin (A) and also preferably have a
sublimation property because they are dispersed well in the
thermoplastic resin (A). Specifically, zinc acetylacetonate,
aluminum acetylacetonate, cobalt acetylacetonate, gallium
acetylacetonate, beryllium acetylacetonate, zinc acetate, and zinc
chloride are preferable, zinc acetylacetonate, aluminum
acetylacetonate, zinc acetate, and zinc chloride are more
preferable, and zinc acetylacetonate is furthermore preferable.
The compounding amount of a metal compound (B) is 0.001 to 50 parts
by mass, preferably 0.01 to 20 parts by mass, and more preferably
0.1 to 10 parts by mass, with respect to 100 parts by mass of a
thermoplastic resin (A). When the compounding amount of a metal
compound (B) is 0.001 part by mass or more, the molded body
obtained comes to have a high light emission intensity. Also, when
the compounding amount of a metal compound (B) is 50 parts by mass
or less, processing of a gas produced by the decomposition of a
metal compound (B) at the time of heating comes to be easy.
Examples of a polyalkylene glycol compound (C) of the present
invention include, for example, polyalkylene glycols such as
polyethylene glycols, polypropylene glycols, and polytetraethylene
glycols; polyalkylene glycol monoalkyl ethers such as polyethylene
glycol monomethyl ethers; and polyalkylene glycol dialkyl ethers
such as polyethylene glycol dimethyl ethers. This polyalkylene
glycol compound (C) may be used alone, or in combination with two
or more kinds.
Among these polyalkylene glycol compounds (C), polyalkylene glycols
and polyalkylene glycol monoalkyl ethers are preferable because a
metal compound (B) is dispersed well. As the alkylene group,
ethylene group, propylene group, and tetraethylene group are more
preferable.
The alkylene group of a polyalkylene glycol compound (C) of the
present invention may have the carbon number of 1 to 20, and may be
linear or branched.
The mass average molecular weight of a polyalkylene glycol compound
(C) is preferably 100 to 200,000, and more preferably 1,000 to
50,000. When the mass average molecular weight of a polyalkylene
glycol compound (C) is 100 or more, the molded body obtained comes
to have a good mechanical property. Also, when the mass average
molecular weight of a polyalkylene glycol compound (C) is 200,000
or less, it comes to have a good compatibility with a thermoplastic
resin (A), whereby the metal oxide comes to be dispersed well in
the molded body and the molded body obtained comes to have a high
light emission intensity.
The compounding amount of a polyalkylene glycol compound (C) is
0.001 to 30 parts by mass, preferably 0.1 to 25 parts by mass, and
more preferably 1.0 to 20 parts by mass, with respect to 100 parts
by mass of a thermoplastic resin (A). When the compounding amount
of a polyalkylene glycol compound (C) is 0.001 part by mass or
more, the molded body obtained comes to have a high light emission
intensity. Also, when the compounding amount of a polyalkylene
glycol compound (C) is 30 parts by mass or less, it comes to have a
good compatibility with a thermoplastic resin (A), and the molded
body obtained comes to have a good mechanical property and a good
thermal property.
The compounding ratio of a metal compound (B) and a polyalkylene
glycol compound (C) can appropriately be selected in view of the
light emission property of a molded body obtained. In 100 mass % of
the total of a metal compound (B) and a polyalkylene glycol
compound (C), it is preferable that the metal compound (B) is 0.1
to 50 mass % and the polyalkylene glycol compound (C) is 50 to 99.9
mass %. It is more preferable that the metal compound (B) is 0.5 to
40 mass % and the polyalkylene glycol compound (C) is 60 to 99.5
mass %. It is furthermore preferable that the metal compound (B) is
1 to 30 mass % and the polyalkylene glycol compound (C) is 70 to 99
mass %.
When the compounding ratio of a metal compound (B) is 0.1 mass % or
more, the molded body obtained comes to have a high light emission
intensity. Also, when the compounding ratio of a metal compound (B)
is 50 mass % or less, the molded body obtained comes to have a good
mechanical property and a good thermal property. Also, when the
compounding ratio of a polyalkylene glycol compound (C) is 50 mass
% or more, the molded body obtained comes to have a good mechanical
property and a good thermal property. Also, when the compounding
ratio of a polyalkylene glycol compound (C) is 99.9 mass % or less,
the molded body obtained comes to have a high light emission
intensity.
If needed, an additive such as a plasticizer, a lubricant, a
stabilizer, an oxidant inhibitor, an ultraviolet absorber, or a
mold release agent besides a thermoplastic resin (A), a metal
compound (B) and a polyalkylene glycol compound (C) may be
compounded to the composition of the present invention.
A production method of a thermoplastic resin composition of the
present invention is not particularly limited as long as it include
compounding a thermoplastic resin (A), a metal compound (B), and a
polyalkylene glycol compound (C) and heating them at a temperature
of 100 to 320.degree. C. Examples thereof include, for example, a
method in which a thermoplastic resin (A), a metal compound (B),
and a polyalkylene glycol compound (C) are concurrently heated and
mixed; a method in which a thermoplastic resin (A) and a
polyalkylene glycol compound (C) are heated and mixed, and
thereafter a metal compound (B) is heated and mixed; and a method
in which a small amount of a thermoplastic resin (A), and a metal
compound (B) and a polyalkylene glycol compound (C) are heated and
mixed to produce a masterbatch containing the metal compound (B) at
a high concentration, and thereafter a remaining thermoplastic
resin (A) is heated and mixed.
Among these production methods, a method in which a thermoplastic
resin (A) and a polyalkylene glycol compound (C) are heated and
mixed, and thereafter a metal compound (B) is heated and mixed is
preferable because the molded body obtained comes to have a high
light emission intensity.
The thermoplastic resin composition obtained can be pelletized and
used as a molding material.
In a method of heating and mixing, a well-known kneading apparatus
can be used. Examples thereof include, for example, single-screw
extruders, multi-screw extruders having two or more screws, bumbary
mixers, kneaders, and rolls. A gas or the like generated by
decomposition of a metal compound (B) can be removed by vacuum
devolatization using a vent port provided in the apparatus. Also,
heating is carried out under an inert atmosphere or a reductive
atmosphere away from oxidative atmosphere to control the amount of
a defect such as a lattice defect or an oxygen hole of a metal
oxide.
A heating temperature of the present invention can appropriately be
selected from a range of 100 to 320.degree. C. in view of the kind
of a thermoplastic resin (A) and a metal compound (B). For example,
when an acrylic resin or a styrene resin is used as a thermoplastic
resin (A), from the viewpoint of melt viscosity of a thermoplastic
resin (A) and decomposition of a metal compound (B), the
temperature is preferably 180 to 300.degree. C., and more
preferably 200 to 280.degree. C.
A heating time of the present invention can appropriately be
selected in view of the kind of a thermoplastic resin (A) and a
metal compound (B), and in view of a heating temperature. For
example, when an acrylic resin or a styrene resin is used as a
thermoplastic resin (A) and when heating at a temperature of 200 to
280.degree. C. is carried out, from the viewpoint of melt viscosity
of a thermoplastic resin (A) and decomposition of a metal compound
(B), the time is preferably 10 seconds or longer. From the view
point of accelerating decomposition of a metal compound (B), the
time is more preferably 30 seconds or longer. As for the upper
limit of a heating time, from the view point of decomposition of a
thermoplastic resin (A) due to melt kneading, the time is
preferably 60 minutes or shorter, and more preferably 30 minutes or
shorter.
If needed, a thermoplastic resin composition obtained by a
production method of the present invention may include an additive
such as such as a plasticizer, a lubricant, a stabilizer, an
oxidant inhibitor, an ultraviolet absorber, or a mold release
agent.
A molded body and a light emission body of the present invention
can be obtained by molding a thermoplastic resin composition of the
present invention.
As for a molding method, a well-known molding method can be used.
Examples thereof include, for example, injection molding, extrusion
molding, blow molding, inflation molding, vacuum forming,
compression molding, and foaming molding. Also, after having molded
as a film, a biaxially-drawn film, a sheet, an expanded sheet, a
foam bead, or the like, it can be molded as a desired molded
body.
Molding conditions such as temperature, revolution speed, L/D of
the screw, screw configuration, and discharge volume can
appropriately be selected. Dispersion state of a metal oxide in a
molded body can be controlled.
A molded body and a light emission body of the present invention
enable a conversion of an ultraviolet to visible light wavelength
and a control of electroconductivity by the band gap control.
Therefore, they are expected to be applied in an optical material
field or an electronic material field as a topsheet or a sealant of
solar cell, a member for organic electroluminescence, a member for
liquid crystal, a member for lighting, or the like, and in an
agricultural material field as a wavelength conversion sheet.
EXAMPLE
As follows, the present invention is described by Examples, but the
present invention is not limited to these Examples. Note that, in
the Examples, "part(s)" represents "part(s) by mass". The
evaluation of each property shown in the Examples was carried out
by a method shown below.
(1) Measurement of Quantum Yield
The surface (10 mm.times.20 mm) of the molded body obtained (10
mm.times.20 mm.times.2 mm) was set in an integrating sphere of an
absolute quantum yield measuring apparatus (model name: "PE-1100",
made by Otsuka Electronics Co., Ltd.). An excitation light was
selected at 10 nm interval from a range of excitation wavelength of
300 to 420 nm, and a light emission spectrum thereat was measured.
From the data obtained, the internal quantum yield and the external
quantum yield were evaluated. The internal quantum yield was
calculated by dividing the number of light emission photons of the
molding body by the number of photons absorbed in the molded body
among the excitation light irradiated thereto. The external quantum
yield was calculated by dividing the number of light emission
photons of the molding body by the number of photons of the
irradiated excitation light.
(2) Measurement of Light Emission Peak Wavelength
The surface (10 mm.times.20 mm) of the molded body obtained (10
mm.times.20 mm.times.2 mm) was irradiated with an ultraviolet
having a peak wavelength of 365 nm using an ultraviolet laser
(model name: "handy UV lamp SLUV-4", made by AS ONE Corporation,
irradiation intensity at 50 nm distance from a light source: 743
.mu.W/cm.sup.2 (365 nm)) as a light source, and the light emission
peak wavelength of light released from the side surface (10
mm.times.2 mm) of the molded body was measured with an optical thin
film measurement apparatus (model name: "FilmTek 1000", made by
Scientific Computing Int.) as a detector. As for the positions of
the molded body, the light source and the detector, the detector
was placed at an angle of 90.degree. to the optical axis of the
light source, the distance from the light source to the molded body
was 30 cm, and the distance from the molded body to the detector
was 5 cm. Note that, in FIG. 1, the horizontal axis shows
wavelength and the vertical axis shows light emission relative
intensity.
Example 1
100 parts of polymethyl methacrylate (trade name: "VHK", made by
Mitsubishi Rayon Co., Ltd.) as a thermoplastic resin (A) and 2.5
parts of polyethylene glycol monomethyl ether (made by Fluka, mass
average molecular weight: 5000) as a polyalkylene glycol compound
(C) were injected into a small injection molding machine (model
name: "CS-183MMX", made by Custom Scientific Instruments Inc.), and
it was kneaded at a temperature of 220.degree. C. for 1 minute to
obtain a pellet.
The pellet obtained was again injected into the small injection
molding machine, and it was kneaded at a temperature of 220.degree.
C. for 1 minute. After that, 0.5 part of zinc acetylacetonate (made
by Tokyo Chemical Industry Co., Ltd.) was injected, and it was
kneaded at a temperature of 220.degree. C. for 1 minute. After
that, a molded body of 10 mm.times.20 mm.times.2 mm was
obtained.
Examples 2 to 17 and Comparative Examples 1 to 6
These were carried out in the same manner as in Example 1 except
that the kind of the thermoplastic resin (A), the kind and
compounding amount of the metal compound (B), and the kind and
compounding amount of the polyalkylene glycol compound (C) were
changed as shown in Tables 1 to 3, to obtain molded bodies.
The light emission properties of molded bodies obtained in Examples
1 to 17 and Comparative Examples 1 to 6 are shown in Tables 1 to 3.
Also, the light emission spectra of molded bodies obtained in
Example 1 and Comparative Example 3 are shown in FIG. 1.
TABLE-US-00001 TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7
Ex. 8 Ex. 9 Thermoplastic Resin (A) Kind PMMA PMMA PMMA PS PS PS
COP PC PC Part(s) 100 100 100 100 100 100 100 100 100 Metal
Compound (B) Kind Zn(Acac).sub.2 Zn(Acac).sub.2 Zn(Acac).sub.2
Zn(Acac).sub.2 Zn(O- Ac).sub.2 ZnCl.sub.2 Zn(Acac).sub.2
Zn(OAc).sub.2 ZnCl.sub.2 Part(s) 0.5 0.5 0.25 0.5 0.25 0.25 0.5
0.25 0.25 Polyalkylene Glycol Kind PEGMME PEGMME PEG PEGMME PEGMME
PEGMME PEGMME PEGMME PEGMME Compound (C) Molecular 5000 5000 10000
5000 5000 5000 5000 5000 5000 Weight Part(s) 2.5 10.0 10.0 10.0 2.5
2.5 10.0 2.5 2.5 Molding Temperature [.degree. C.] 220 220 220 220
220 220 250 250 250 Internal Excitation 300 1.5 0.2 0.9 3.4 3.4 3.6
0.9 3.9 0.8 Quantum Wavelength [nm] 310 0 0.1 0.6 0.8 2.4 2.0 0.3
2.5 1.9 Yield 320 0.6 0.4 0.7 1.5 2.7 2.4 0.8 2.8 2.0 [%] 330 1.0
0.7 0.7 1.7 2.5 2.1 0.6 2.8 2.4 340 0.6 1.1 1.3 1.8 3.5 2.8 0.7 3.0
2.8 350 0.4 1.6 1.9 2.1 3.9 3.1 0.5 4.2 3.0 360 1.0 2.9 4.1 2.7 4.6
3.8 0.1 5.1 4.1 370 3.5 5.4 6.8 3.8 5.4 4.8 1.3 7.2 5.1 380 8.8 9.9
9.6 4.9 6.0 5.5 0.8 10.5 6.1 390 13.6 13.5 12.8 6.9 7.8 7.8 1.8 9.3
5.4 400 14.4 15.3 13.9 7.1 9.1 8.1 1.9 9.9 5.2 410 16.9 17.7 16.6
7.1 10.6 8.5 1.9 6.6 3.9 420 17.6 17.8 14.2 6.2 5.2 4.9 1.1 5.5 1.8
External Excitation 300 1.4 0.2 0.9 3.1 3.1 3.3 0.9 3.5 0.7 Quantum
Wavelength [nm] 310 0 0.1 0.6 0.7 2.2 1.8 0.3 2.2 1.7 Yield 320 0.6
0.4 0.7 1.4 2.4 2.1 0.7 2.5 1.7 [%] 330 1.0 0.6 0.6 1.6 2.2 1.8 0.6
2.4 1.9 340 0.5 1.0 1.1 1.6 3.0 2.5 0.7 2.4 2.0 350 0.4 1.5 1.5 1.9
3.3 2.7 0.5 3.2 2.1 360 0.9 2.7 3.0 2.4 3.7 3.2 0.1 3.6 2.5 370 3.2
5.1 4.4 3.3 4.0 3.9 1.2 4.7 2.9 380 7.1 9.0 5.6 4.1 3.8 4.2 0.7 6.1
3.1 390 9.9 12.0 7.0 5.7 4.1 5.3 1.6 4.9 2.6 400 9.7 13.3 7.0 5.6
4.1 5.0 1.6 4.7 2.3 410 10.6 14.9 7.8 5.4 4.3 4.8 1.5 2.9 1.6 420
10.0 14.0 6.0 4.4 1.8 2.5 0.9 2.2 0.7
TABLE-US-00002 TABLE 2 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15
Ex. 16 Ex. 17 Thermoplastic Resin (A) Kind PMMA PMMA PMMA PMMA PMMA
PMMA PMMA PMMA Part(s) 100 100 100 100 100 100 100 100 Metal
Compound (B) Kind Zn(Acac).sub.2 Zn(Acac).sub.2 Zn(Acac).sub.2
Zn(Acac).sub.2 Zn(A- cac).sub.2 Zn(Acac).sub.2 Zn(Acac).sub.2
Zn(Acac).sub.2 Part(s) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Polyalkylene
Glycol Kind TPG TPG PTG PTG PPG PPG PEGMME PEGMME Compound (C)
Molecular 192 192 2000 2000 4000 4000 350 2000 Weight Part(s) 2.5
5.0 2.5 5.0 2.5 5.0 2.5 2.5 Molding Temperature [.degree. C.] 220
220 220 220 220 220 220 220 Internal Excitation 300 0 0 1.1 0.8 0
0.6 0.8 0.8 Quantum Wavelength 310 0.1 0.1 0.3 0.6 0 0 0 0.2 Yield
[nm] 320 0.1 0.1 0.4 0.5 0.2 0.7 0.2 0 [%] 330 0.5 0 0.7 1.0 0.3
1.0 0.2 0 340 0.2 0 0.7 0.7 0.1 1.1 0.3 0.2 350 0.1 0 1.0 1.7 0 1.3
0.7 0.2 360 0.5 0 1.1 2.2 0.9 2.7 1.0 0.6 370 1.7 1.8 3.4 5.9 2.1
6.5 2.8 1.4 380 6.2 6.9 9.0 11.3 6.6 11.1 11.7 7.5 390 14.9 15.1
13.8 17.4 9.7 16.6 20.4 18.9 400 18.3 17.0 10.9 20.8 11.5 18.2 21.6
23.6 410 19.2 18.6 18.7 24.1 14.2 19.2 26.6 26.5 420 18.0 23.0 12.9
24.3 13.5 20.7 25.7 27.2 External Wxcitation 300 0 0 1.0 0.8 0 0.6
0.8 0.7 Quantum Wavelength 310 0.1 0.1 0.3 0.6 0 0 0 0.2 Yield [nm]
320 0.1 0.1 0.4 0.5 0.2 0.6 0.2 0 [%] 330 0.4 0 0.6 0.9 0.3 1.0 0.2
0 340 0.2 0 0.7 0.7 0.1 1.0 0.3 0.2 350 0 0 0.9 1.6 0 1.2 0.7 0.2
360 0.5 0 1.0 2.1 0.8 2.5 1.0 0.6 370 1.3 1.4 2.8 5.4 1.8 5.8 2.5
1.3 380 3.0 3.3 5.8 9.9 4.2 8.9 7.7 6.3 390 5.2 5.1 7.5 14.3 5.1
12.3 10.9 13.2 400 5.4 4.6 5.1 16.0 5.1 12.4 10.4 15.1 410 5.0 4.4
7.7 17.2 5.5 12.1 11.6 15.6 420 4.0 4.6 4.5 15.4 4.4 11.6 9.6
13.9
TABLE-US-00003 TABLE 3 Com. Ex. 1 Com. Ex. 2 Com. Ex. 3 Com. Ex. 4
Com. Ex. 5 Com. Ex. 6 Thermoplastic Resin (A) Kind PMMA PMMA PMMA
PS COP PC Part(s) 100 100 100 100 100 100 Metal Compound (B) Kind
-- Zn(Acac).sub.2 Zn(Acac).sub.2 Zn(Acac).sub.2 Zn(Acac).sub.2 Z-
n(Acac).sub.2 Part(s) -- 0.25 0.5 0.5 0.5 0.25 Polyalkylene Glycol
Kind -- -- -- -- -- -- Compound (C) Molecular -- -- -- -- -- --
Weight Part(s) -- -- -- -- -- Molding Temperature [.degree. C.] 220
220 220 220 250 250 Internal Excitation 300 0 0.3 0 0 0 1.3 Quantum
Wavelength 310 0 0 0 0 0 1.2 Yield [nm] 320 0 0 0 0 0 1.4 [%] 330 0
0 0 0 0 1.4 340 0 0.1 0 0 0.1 1.5 350 0 0 0 0.1 0.2 1.8 360 0 0 0.1
0 0 2.1 370 0 0.5 0.2 0 0.1 3.1 380 0 2.8 1.1 0.7 0.4 4.8 390 0 6.5
3.9 2.3 0.7 4.2 400 0 8.8 4.8 2.8 1.1 4.9 410 0 10.0 6.2 2.6 0.4
3.3 420 0 9.7 5.7 2.6 0.6 2.7 External Excitation 300 0 0.3 0 0 0
1.2 Quantum Wavelength 310 0 0 0 0 0 1.1 Yield [nm] 320 0 0 0 0 0
1.2 [%] 330 0 0 0 0 0 1.2 340 0 0.1 0 0 0.1 1.2 350 0 0 0 0.1 0.2
1.3 360 0 0 0.1 0 0 1.5 370 0 0.5 0.2 0 0.1 2.0 380 0 1.8 0.9 0.5
0.3 2.8 390 0 2.7 2.4 1.3 0.6 2.2 400 0 3.0 2.5 1.2 0.8 2.3 410 0
3.0 2.9 1.0 0.3 1.4 420 0 2.4 2.3 0.8 0.4 1.1 Note that, the
abbreviations described in Tables 1 to 3 represent the following
compounds. "PMMA": polymethyl methacrylate (trade name: VHK, made
by Mitsubishi Rayon Co., Ltd.) "PS": polystyrene (trade name: Toyo
styrol G200C, made by Toyo Stylene Co., Ltd.) "COP": cycloolefin
resin (trade name: ZEONOR 1420R, made by Zeon Corporation) "PC":
polycarbonate resin (trade name: Panlite L-1250WP, made by Teijin
Chemicals Ltd.) "Zn(Acac).sub.2": zinc acetylacetonate
"Zn(OAc).sub.2": zinc acetate "ZnCl.sub.2": zinc chloride "PEGMME":
polyethylene glycol monomethyl ether "PEG": polyethylene glycol
"TPG": tripropylene glycol "PTG": polytetraethylene glycol (trade
name: UNIOL PB-2000R, made by NOF Corporation) "PPG": polypropylene
glycol ((trade name: UNIOL D-4000, made by NOF Corporation)
As is clear from Tables 1 to 3, the molded bodies obtained in
Examples 1 to 17 had a high light emission intensity. The molded
bodies obtained in Comparative Examples 2 to 6, in which no
polyalkylene glycol compound (C) was compounded, had a low light
emission intensity. The molded body obtained in Comparative Example
1, in which no metal compound (B) and polyalkylene glycol compound
(C) were compounded, did not emit light.
INDUSTRIAL APPLICABILITY
A molded body and a light emission body of the present invention
enable a conversion of an ultraviolet to visible light wavelength
and a control of electroconductivity by the band gap control, and
are expected to be applied in an optical material field or an
electronic material field, such as a solar cell, an organic
electroluminescence, a liquid crystal, and the like.
* * * * *